Acrylic polymer compositions with crystalline side chains and processes for their preparation

ABSTRACT

Acrylic polymer compositions with crystalline side chains are disclosed. Solution polymerization, aqueous suspension polymerization, and aqueous dispersion polymerization processes for the preparation of the acrylic polymer compositions with crystalline side chains are also disclosed. Methods of use for the acrylic polymer compositions with crystalline side chains, including dry powder coatings; wax replacements in floor polishes and wood coatings; nonwoven and textile coatings; adhesives; and hot melt adhesives are also disclosed.

[0001] Acrylic polymers have many useful properties such as durability,flexibility in composition and glass transition temperature (“Tg”),weather resistance, adhesion to polar substrates, and compatibility withmany polar polymers and inoganic components. While each of theproperties may be desirable, it is difficult to obtain all of them inone polymer. One often needs to sacrifice one property to gain anotherbecause the properties of the polymer depend on the polymer'scomposition, molecular weight, and Tg. For example, a low Tg may bedesirable for a polymer composition which would be useful in adhesiveapplications, but the low Tg polymer may not provide good durability.

[0002] In addition, because acrylic polymers are generally amorphous,they are not effective in all applications where crystallinity isdesired. They do not adhere well to most non-polar substrates such aspolyolefins. Amorphous acrylic polymers also are inferior in terms ofwater resistance and durability as compared with polyolefins. Therefore,there is a need for low cost polymer compositions which providedurability, flexibility in composition and Tg, weather resistance,adhesion to polar and non-polar substrates, compatibility with polarpolymers and inoganic components, and water resistance.

[0003] Previous methods to achieve a combination of desired propertiesof acrylic polymers and olefin polymers in “one” polymer includedphysically mixing an acrylic polymer and an olefin polymer orcopolymerizing an olefin monomer and an acrylic monomer. These methodshave not been successful. Physical mixing of acrylic polymers andpolyolefins does not usually yield useful compositions because the twopolymers are incompatibile. Copolymerizing an olefin monomer and anacrylic monomer is difficult because there is poor reactivity betweenthe two monomers. In addition, copolymerization of two monomers usuallyresults in a composition with an average of the combined properties ofeach homopolymer rather than enhanced properties.

[0004] U.S. Pat. No. 5,387,450 ('450) tries to solve the problem. Thispatent discloses polymer compositions which contain as polymerized unitscrystallizable side chain monomers and are useful as adhesives. Belowthe melting temperature of the crystallizable side chain, the polymer isnon-tacky. Above the melting temperature of the crystallizable sidechain, the polymer turns into a tacky adhesive. The compositions arerequired to contain at least 50 weight percent of a crystallizable sidechain monomer. The crystallizable side chain monomers are acrylates ormethacrylates with 14 to 22 carbon atoms as side chains. Even thoughthis patent provides a route to achieve some of the properties discussedabove, there are still several problems unresolved by the patent. Thecrystallizable side chain monomers of the patent have lower meltingpoints and are more soluble in organic solvents than crystallizable sidechain monomers with more carbon atoms in the side chains. Therefore, oneproblem is that the patent does not address how to processcrystallizable side chain monomers with more carbon atoms in the sidechains, which require higher temperatures to melt and are less solublein organic solvents. Another problem is that crystallizable side chainmonomers are relatively new and due to their special structure areestimated to cost several times more than the other monomericcomponents. For these reasons, it is desirable to minimize the amount ofcrystallizable side chain monomer in one polymer and still achieve theproperties described above. Despite the disclosure of '450, there isstill a need for low cost polymer compositions which provide durability,flexibility in composition and Tg, weather resistance, adhesion to polarand non-polar substrates, compatibility with polar polymers and inoganiccomponents, and water resistance.

[0005] To provide the desired polymer compositions, the inventors haveprepared polymers containing an acrylic backbone with less than 50percent by weight synthetic wax monomer (“SWM”). The SWM containscrystalline polyethylene side chains and therefore is a crystallizableside chain monomer. One benefit from the copolymers of this invention isthat one may achieve physical crosslinking through the association ofone polymer component. This association can be crystallization or simplyphase separation. The physical crosslinks that form are not permanentand can be “decrosslinked” by heating. Through such physicalcrosslinking, the backbone polymer matrix forms a network likestructure, yet it can be fully decrosslinked when the polymer is heatedabove the melting temperature of the association blocks. Formation of anetwork structure helps to prevent loss of the physical properties whenone has to reduce the molecular weight or Tg of the backbone polymer forprocessing or flexibility reasons.

[0006] In a first aspect, the present invention provides a polymerincluding as polymerized units:

[0007] A) from 1 to less than 50 percent by weight of a synthetic waxmonomer of formula I:

[0008] wherein

[0009] R₁ is selected from H and CH₃,

[0010] R₂ is selected from H and C₁-C₅ alkyl,

[0011] R₃ is selected from H and CH₃,

[0012] n=9-115, preferably 12-90, more preferably 15-50, and

[0013] m=0-1370, preferably 0-65, more preferably 0-50; and

[0014] B) from 50 to 99 percent by weight of at least one secondmonomer.

[0015] Previously, it has been difficult to prepare the polymercompositions described above. For example, the '450 patent describedabove utilized a one shot solution polymerization reaction to polymerizethe monomers. For a solution process, it is desirable to be able togradually add the SWM to the polymerization kettle because it isbelieved that the SWM will be more evenly incorporated into the polymer.Emulsion and suspension processes are desirable because they allow for areduction of or elimination of organic solvents. The '450 patent did notaddress these concerns. Consequently, there is a continuing need forprocesses to prepare polymers containing SWMs.

[0016] The inventors have provided several approaches to preparingpolymers containing SWMs. In one approach, a SWM slurry is preparedprior to polymerization of the SWM. The slurry may be used to preparesolution or suspension polymers. For a solution process, the slurry maybe combined with additional monomers or organic solvent and co-fed to areactor with an initiator. For a suspension process, the slurry iscombined with an initiator and an aqueous solution and polymerized.

[0017] In a second aspect, the present invention provides a method ofpreparing a polymer from a slurry by: 1) forming a slurry by cooling asolution containing a synthetic wax monomer and a solvent; 2) forming areaction mixture by admixing at least one second monomer with theslurry; and 3) polymerizing the reaction mixture in the presence of aninitiator.

[0018] In a third aspect, the present invention provides a method ofpreparing a polymer from an emulsion by dissolving a synthetic waxmonomer in at least one second monomer to form a solution, admixingwater and at least one surfactant to provide a second solution, forminga monomer emulsion by admixing the first and second solutions, providinga reactor with heated water, and polymerizing the monomer emulsion byadding the monomer emulsion and at least one initiator to the reactor.

[0019] In a fourth aspect, the present invention provides a method ofcoating including applying a composition containing the polymer of theinvention to a substrate.

[0020] As used throughout this specification, by the term (meth)acrylicacid is meant both acrylic acid and methacrylic acid. Likewise, as usedthroughout this specification, by the term (meth)acrylate is meant bothacrylate and methacrylate esters.

[0021] The SWMs of this invention are C₂₄ to C₈₀, preferably C₃₀ to C₅₀ethylenically unsaturated (meth)acrylate monomers or ethoxylates thereofand are formed from C₂₄ to C₈₀ synthetic wax alcohols. Generally, theSWMs are formed by reacting a C₂₄ to C₈₀ synthetic wax alcohol orethoxylate thereof with an alkyl (meth)acrylate in the presence of azirconium catalyst and suitable inhibitor, although they may be made byother processes well known in the art. Suitable alcohols or ethoxylatesare available from Baker Petrolite, Inc. Houston, Tex. as Unilin™ orUnithox™ products. Suitable examples of SWMs include the acrylate ormethacrylate esters of Unilin 350, Unilin 450, Unilin 550, Unilin 700,and Unithox 450. The amount of SWM in the polymer is typically from 1%to less than 50%, preferably 3% to 45%, more preferably 4% to 40%, mostpreferably 5% to 35% by weight, based on the total weight of the polymerof this invention.

[0022] The at least one second monomer may be an ethylenicallyunsaturated monomer. Suitable ethylenically unsaturated monomers includeacrylic and methacrylic acid and esters thereof. Generally, the(meth)acrylates are C₁ to C₂₄ (meth)acrylates. The (meth)acrylate istypically from 50% to 99%, preferably 55% to 97%, more preferably 60% to96% by weight, based on the total weight of the polymer of thecomposition of this invention. Examples of the alkyl (meth)acrylate aremethyl methacrylate (MMA), ethyl methacrylate (EMA), methyl and ethylacrylate, propyl methacrylate, butyl methacrylate (BMA) and acrylate(BA), isobutyl methacrylate (IBMA), hexyl and cyclohexyl methacrylate,cyclohexyl acrylate, 2-ethylhexyl acrylate (EHA), 2-ethylhexylmeth-acrylate, octyl methacrylate, decyl methacrylate, isodecylmethacrylate (IDMA, based on branched (C₁₀)alkyl isomer mixture),undecyl methacrylate, dodecyl methacrylate (also known as laurylmethacrylate), tridecyl methacrylate, tetradecyl methacrylate (alsoknown as myristyl methacrylate), pentadecyl methacrylate,dodecyl-pentadecyl methacrylate (DPMA), a mixture of linear and branchedisomers of dodecyl, tridecyl, tetradecyl and pentadecyl methacrylates;and lauryl-myristyl methacrylate (LMA), a mixture of dodecyl andtetradecyl methacrylates, hexadecyl methacrylate, heptadecylmethacrylate, octadecyl methacrylate, nonadecyl methacrylate, cosylmethacrylate, eicosyl methacrylate, cetyl-eicosyl methacrylate (CEMA), amixture of hexadecyl, octadecyl, cosyl and eicosyl methacrylate; andcetyl-stearyl methacrylate (SMA), and a mixture of hexadecyl andoctadecyl methacrylate. Mixtures of one or more (meth)acrylates may alsobe used.

[0023] Another class of suitable ethylenically unsaturated monomersuseful as the at least one second monomer are vinylaromatic monomerswhich include, among others, styrene (Sty), α-methylstyrene,vinyltoluene, p-methylstyrene, ethylvinylbenzene, vinylnaphthalene,vinylxylenes, and the like. The vinylaromatic monomers can also includetheir corresponding substituted counterparts, such as halogenatedderivatives, i.e., containing one or more halogen groups, such asfluorine, chlorine or bromine; and nitro, cyano, alkoxy, haloalkyl,carbalkoxy, carboxy, amino, alkylamino derivatives and the like. Thevinylaromatic monomers may be used at levels of from 0% to 50%,preferably 0% to 30% by weight, based on the total weight of the polymerof the composition of this invention.

[0024] Another class of suitable ethylenically unsaturated monomers thatmay be useful as the at least one second monomer are nitrogen-containingring compounds and their thioanalogs, such as vinylpyridines such as2-vinylpyridine or 4-vinylpyridine, and lower alkyl (C₁-C₈) substitutedC-vinyl pyridines such as: 2-methyl-5-vinyl-pyridine,2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine,2,3-dimethyl-5-vinyl-pyridine, 2-methyl-3-ethyl-5-vinylpyridine;methyl-substituted quinolines and isoquinolines, N-vinylcaprolactam,N-vinylbutyrolactam, N-vinylpyrrolidone, vinyl imidazole, N-vinylcarbazole, N-vinyl-succinimide, acrylonitrile, o-, m-, orp-aminostyrene, maleimide, N-vinyl-oxazolidone, N,N-dimethylaminoethyl-vinyl-ether, ethyl-2-cyano acrylate, vinyl acetonitrile,N-vinylphthalimide. Also included are N-vinyl-thio-pyrrolidone, 3methyl-1-vinyl-pyrrolidone, 4-methyl-1-vinyl-pyrrolidone,5-methyl-1-vinyl-pyrrolidone, 3-ethyl-1-vinyl-pyrrolidone,3-butyl-1-vinyl-pyrrolidone, 3,3-dimethyl-1-vinyl-pyrrolidone,4,5-dimethyl-1-vinyl-pyrrolidone, 5,5-dimethyl-1-vinyl-pyrrolidone,3,3,5-trimethyl-1-vinyl-pyrrolidone, 4-ethyl-1-vinyl-pyrrolidone,5-methyl-5-ethyl-1-vinyl-pyrrolidone,3,4,5-trimethyl-1-vinyl-pyrrolidone, and other lower alkyl substitutedN-vinyl-pyrrolidones. The nitrogen-containing ring compounds and theirthioanalogs may be used at levels of from 0% to 50%, preferably 0% to30% by weight, based on the total weight of the polymer of thecomposition of this invention.

[0025] Another class of suitable ethylenically unsaturated monomers thatmay be useful as the at least one second monomer are substitutedethylene monomers, such as vinyl acetate, vinyl chloride, vinylfluoride, vinyl bromide, vinylidene chloride, vinylidene fluoride,vinylidene bromide, acrylonitrile, methacrylonitrile, acrylic acid (AA)and corresponding amides and esters, methacrylic acid (MAA) andcorresponding amides and esters. The substituted ethylene monomers maybe used at levels of from 0% to 50%, preferably 0% to 30% by weight,based on the total weight of the polymer of the composition of thisinvention.

[0026] Another class of acrylic and methacrylic acid derivatives thatmay be useful as the at least one second monomer is represented bysubstituted alkyl acrylate and methacrylate and substituted acrylamideand methacrylamide monomers. Examples include (meth)acrylates whereinthe alkyl group is substituted with halogen, such as fluorine, chlorineor bromine; and nitro, cyano, alkoxy, haloalkyl, carbalkoxy, carboxy,amino, alkylamino derivatives, glycidyl (meth)acrylate and the like. Thesubstituted alkyl acrylate and methacrylate and substituted acrylamideand methacrylamide monomers may be used at levels of from 0% to 50%,preferably 0% to 30% by weight, based on the total weight of the polymerof the composition of this invention.

[0027] Each of the substituted monomers that may be useful as the atleast one second monomer can be a single monomer or a mixture havingdifferent numbers of carbon atoms in the alkyl portion. The alkylportion of each monomer can be linear or branched.

[0028] Hydroxyalkyl (meth)acrylate monomers may also be useful in thisinvention as the at least one second monomer. Among the hydroxyalkylmethacrylate and acrylate monomers suitable for use in the presentinvention are 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethylacrylate(HEA), 2-hydroxypropyl methacrylate, 1-methyl-2-hydroxyethylmethacrylate, 2-hydroxy-propyl acrylate, 1-methyl-2-hydroxyethylacrylate, 2-hydroxybutyl methacrylate and 2-hydroxybutyl acrylate. Thehydroxyalkyl (meth)acrylate monomers may be used at levels of from 0% to50%, preferably 0% to 30% by weight, based on the total weight of thepolymer of the composition of this invention.

[0029] Additional examples of substituted (meth)acrylate monomers usefulas the at least one second monomer are those alkyl methacrylate andacrylate monomers with a dialkylamino group in the alkyl radical, suchas dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate and thelike.

[0030] Other examples of substituted (meth)acrylate monomers useful asthe at least one second monomer are nitrogen-containing ring compounds(previously described) and dialkylaminoalkyl methacrylamide andacrylamide monomers, such as N,N-dimethylaminoethyl methacrylamide,N,N-dimethyl-aminopropyl methacrylamide, N,N-dimethylaminobutylmethacrylamide, N,N-diethylaminoethyl methacrylamide,N,N-diethylaminopropyl methacrylamide, N,N-diethylaminobutylmethacrylamide, N-(1,1-dimethyl-3-oxobutyl) acrylamide,N-(1,3-diphenyl-1-ethyl-3-oxobutyl) acrylamide,N-(1-methyl-1-phenyl-3-oxobutyl) methacrylamide, and 2-hydroxyethylacrylamide, N-methacrylamide of aminoethyl ethylene urea, N-methacryloxyethyl morpholine, N-maleimide of dimethylaminopropylamine and the like.

[0031] Ethylenically unsaturated acid monomers such as, for exampleacrylic acid, methacrylic acid, crotonic acid, phosphoethylmethacrylate, 2-acrylamido-2-methyl-1-propanesulfonic acid, sodium vinylsulfonate, itaconic acid, fumaric acid, maleic acid, monomethylitaconate, monomethyl fumarate, monobutyl fumarate, and maleic anhydridemay also be used as the at least one second monomer in the polymers ofthis invention. The ethylenically unsaturated acid monomers may be usedat from 0%-20% by weight, based on the weight of the polymer.

[0032] The polymer of this invention can be linear, branched orpartially crosslinked. It can be post crosslinkable. By postcrosslinkable is meant that the polymer may have reactive groups whichdo not react during polymerization, but may react after polymerizationto provide crosslinking. The physical form of the polymer may bepellets, beads, emulsion, solution, or chunks. The polymer may have amolecular weight of from 5,000 to 5,000,000, preferably 10,000 to2,000,000, more preferably 20,000 to 1,000,000 as determined by gelpermeation chromatography (“GPC”). The polymer may have a melting pointof from 20° C. to 110° C. as determined by differential scanningcalorimetry (“DSC”). Alternate processes may be used to prepare thepolymer of this invention. Suitable processes include solutionpolymerization, aqueous suspension polymerization, and aqueousdispersion polymerization (both batch and semi-continuous).

[0033] In the slurry process of the invention, a slurry is formed bycooling a solution containing the SWM and a solvent until the SWMprecipitates out of solution as crystals. This process may be used forsolution or suspension polymerization. For a solution processembodiment, the SWM may be admixed with an organic solvent and heateduntil the SWM is melted and dissolved, and then cooled with agitation.Suitable solvents include, but are not limited to hexane, heptane,xylene, toluene, ethyl acetate, butyl acetate, hexanol, heptanol,octanol, decane, decalin, and the like. After cooling, other monomersmay be added. Suitable monomers include (meth)acrylic acid, esters of(meth)acrylic acid, (meth)acrylic amides, vinyl aromatic monomers,substituted ethylene monomers, functional monomers with a postcrosslinkable group, multifunctional monomers, and mixtures thereof. Thecooled slurry can be gradually added to a reaction kettle in thepresence of an initiator to form solution polymers.

[0034] For a suspension process embodiment, the SWM may be admixed withother monomers and an aqueous solution and heated until the SWM ismelted and dissolved in the organic phase. The mixture is cooled belowthe temperature at which polymerization will be initiated and theninitiator is added. The mixture is stirred to evenly incorporate theinitator into the organic phase. The cooled mixture containing theinitiator is then heated and the stirring rate is increased to form adispersion and to initiate polymerization. The aqueous solution maycontain a suspending agent/dispersant for stabilizing polymerizingdroplets. The suspending agent/dispersant may be used at from 0.01% to5% by weight, based on the total weight of the mixture. Suitablesuspending agents/dispersants include polyalkyldimethylammoniumchloride, polyvinylalcohol, hydroxyethylcellulose,hydroxypropylcellulose or various other cellulose materials, polyvinylpyrrolidone, natural gum, powdered dispersants, and the sodium salt ofpoly(meth)acrylic acid homopolymer or copolymers.

[0035] In the dispersion process of the invention, a solution containinga SWM in at least one second monomer is provided. In the process, thesolution may be obtained by heating an admixture of a SWM in at leastone second monomer until the synthetic wax monomer melts and dissolvesas described above. The solution may be admixed with a second aqueoussurfactant solution to create a monomer emulsion.

[0036] In one embodiment of the dispersion process, the at least onesecond monomer of the first solution may be selected from the monomersdescribed above, including (meth)acrylic acid, esters of (meth)acrylicacid, (meth)acrylic amides, vinyl aromatic monomers, substitutedethylene monomers, functional monomers with a post crosslinkable group,multifunctional monomers, and mixtures thereof.

[0037] In a second embodiment of the dispersion process, the at leastone second monomer of the first solution may be selected from a SWMcontaining polyethylene blocks. In this case, the second SWM acts as anaqueous dispersant for the first SWM. SWMs such aspoly(ethylene-b-ethyleneoxide)-acrylate (Unithox™ 450 acrylate), may besuitable for these purposes. Similar low molecular weight diblockpolymers without the polymerizable (meth)acrylate end group, such aspoly(ethylene)-b-poly(ethyleneoxide)-OH (Unithox198 ethoxylate), mayalso be used as dispersants. The dispersants may be used at from 0% to20% by weight, preferably 1% to 15% by weight, more preferably 2% to 10%based on the total weight of the first synthetic wax monomer.

[0038] For both dispersion process embodiments, the second solution maybe an aqueous surfactant solution. Surfactants may be used at from 0.1%to 5% by weight, based on the total weight of the monomer mixture. Thesurfactants can be anionic, nonionic or cationic. Anionic surfactants ora combination of an anionic surfactant with a nonionic surfactant arepreferred.

[0039] In the processes of the invention, a reaction mixture is formedby admixing at least one second monomer with the SWM. The amount of theat least one second monomer admixed with the SWM ranges from 50% to 99%,preferably 60% to 97%, more preferably 65% to 95% by weight based on theweight of the SWM. The at least one second monomer to be admixed withthe synthetic wax monomer may be selected from the monomers describedabove, including (meth)acrylic acid, esters of (meth)acrylic acid,(meth)acrylic amides, vinyl aromatic monomers, substituted ethylenemonomers, functional monomers with a post crosslinkable group,multifunctional monomers, and mixtures thereof.

[0040] In the processes of the invention, the monomers may bepolymerized by co-feeding the reaction mixture and an initiator to areactor or batch polymerizing a reaction mixture in a reactor at atemperature sufficient to initiate polymerization. Typically, thereactor is at a temperature from 75° C. to 110° C. The initiator ispreferably water insoluble and may be selected from peroxyesters,dialkylperoxides, alkylhydroperoxides, persulfates, azoinitiators, redoxinitiators and other known free radical inititators. Part of theinitiator is incorporated into the polymer as end groups. The amount ofthe initiator used is generally from 0.05% to 5% by weight, based on theweight of total monomer.

[0041] The dispersion process will yield a latex polymer. The polymerfrom the latex can be isolated by any method known in the art, such asspray drying, freeze drying, or coagulation. The suspension process willyield polymer beads. The polymer beads can be isolated by filtration.The solution process will yield a homogeneous polymer solution when agood solvent is used. Toluene, xylene, and decalin are examples of goodsolvents. If one wants to isolate the polymer from solution, one woulduse a poor solvent. By poor solvent is meant that the polymer is solublein the solvent at high temperature, but insoluble at low temperature.Examples of poor solvents are heptane, hexane, or other saturated alkanesolvents. The polymer may be isolated by cooling of the solutionfollowed by filtration. Where a solid is isolated, the solid may containsolvent and may be vacuum dried at ambient temperature to give neatpolymer chunks. The crumbly solid may also be diluted in solvent,re-heated to form a solution, cooled with stirring, vacuum filtered, andair dried on a Buchner funnel to yield solid polymer chunks.

[0042] Chain transfer agents may be used for regulating molecular weightin the processes to prepare the polymers of this invention. Suitablechain transfer agents include organic thiol compounds such as n-dodecylmercaptan and the like. The chain transfer agent may be used at 0% to10% by weight of the total monomer mixture. When used in the processesto prepare the polymers of this invention, part of the chain transferagent structure is incorporated into the polymer as an end group.

[0043] A salt may be used in suspension processes of preparing thepolymers of this invention to reduce the solubility of organic monomersin the aqueous phase. The salt may be used at from 0% to 8% by weight,based on the total weight of the mixture. Suitable salts include sodiumchloride, potassium chloride and the like.

[0044] Organic solvents may be used in suspension processes of preparingthe polymers of this invention for improving the solubility of thesynthetic wax (meth)acrylate in the other monomers. The organic solventsmay be used at from 0% to 200% by weight, preferably 0% to 100% byweight, based on the total weight of the synthetic wax (meth)acrylate.

[0045] A buffer may be useful in dispersion processes to prepare thepolymers of this invention to maintain the pH of the aqueous phase.Suitable buffers include sodium, potassium, and ammonium salts ofcarbonate, bicarbonate, acetate, phosphate, and borate. The buffers maybe used at from 0% to 5% based on the total weight of the composition.

[0046] Sodium nitrite or sodium perborate may be useful as radicalinhibitors in dispersion processes to prepare the polymers of thisinvention to inhibit any undesirable polymerization in the aqueousphase. The radical inhibitors may be used at from 0% to 1% based on thetotal weight of water in the composition.

[0047] The polymers prepared by the process of the invention are usefulin applications such as hot melt adhesives, hot melt sealants/caulks,plastic additives, compatibilizers, textile binders, roof mastics,traffic paints, barrier or protective coatings, powder coatings, waterresistant sealer for wood and masonry materials, floor wax, waterrepellants for textiles, carrier polymers of biocides or other activeingredients in agriculture products.

[0048] For use in the above coating applications, the polymer may beformulated with materials such as binders, pigments, additives andfillers to prepare coating compositions suitable for each application.The coating composition is then applied to a substrate and then dried.The coating composition may be applied by spraying, dipping, or othermethods known in the art. Suitable substrates include vinyl,polypropylene, metal, wood, cement, paper, nonwovens, textiles, andother substrates known in the art. The coating composition may be driedunder ambient conditions. Forced air may be utilized to aid in thedrying of the coating composition. Heat may also be utilized in thedrying of the coating composition. The forced air may be heated, or thecoated substrate may be placed in a heated oven. The temperature of theheat may range from 35° C. to 110° C.

[0049] The polymers of this invention may also be useful as dry powdercoating compositions. For dry powder coating compositions, the polymeris isolated as a solid by the techniques described above. The drypolymer may be ground to a powder by any milling equipment suitable forproducing particles in the size range of 0.1 to 50 microns, morepreferably 0.25 microns to 35 microns, and most preferably from 0.5microns to 25 microns. The particle size may be measured on a Coulter™LS, light scattering, particle size analyzer. Suitable mills areattrition mills, fluid—energy mills, colloid mills, vibratory ball mills(vibro-energy mills), pin mills, ball mills, roller mills, andautogenous and semiautogenous mills. Likewise a combination of millscould be used to possibly increase speed where the first mill reducesparticle size to, for example, 100 to 1000 microns and a second millreduces the particle size further to the desired range. An example wouldbe the initial use of a hammer mill followed by a semiautogenous milllike a Dyno-Mill™ from CB Mills Inc (Buffalo Grove, Ill.).

[0050] The dry powder may be applied to a substrate, heated to form afilm, and cooled. Suitable substrates include vinyl, polypropylene,metal, wood, cement, paper, nonwovens, textiles, and other substratesknown in the art. The dry polymer powder may be heated at temperaturesranging from 60° C. to 150° C. to form a film. The film may then becooled either by storage at ambient temperature or by the use of cooledforced air.

[0051] The polymer may also be useful as an adhesive. For adhesiveapplications, a first polymer coated substrate is formed by applying thepolymer to a substrate such as vinyl, polypropylene, metal, wood,cement, or paper. The polymer may be in the form of a liquid or a solid.For a solid polymer, the polymer is then heated to the melting point ofthe polymer. A second substrate may then be applied to the first polymercoated substrate. The second substrate may be selected from vinyl,polypropylene, metal, wood, cement, paper, or release paper. The polymeris then dried or cooled. The polymer may be dried under ambientconditions. Forced air may be utilized to aid in the drying of thecoating composition. Heat may also be utilized in the drying of thecoating composition. The forced air may be heated, or the coatedsubstrate may be placed in a heated oven. The temperature of the heatmay range from 35° C. to 110° C. The polymer may be cooled either bystorage at ambient temperature or by the use of cooled forced air.

[0052] The following examples are intended to demonstrate the polymer ofthe invention, the process of the invention, alternate processes toprepare the polymer of the invention, and the usefulness of the polymerof the invention in various applications. The following abbreviationsapply throughout the examples:

[0053] SWM 1=Unilin™ 550MA (C₄₀ (average) methacrylate)

[0054] SWM 2=Unilin™ 550A (C₄₀ (average) acrylate)

[0055] SWM 3=Unilin™ 700MA (C₅₀ (average) methacrylate)

[0056] SWM 4=Unilin™ 700A (C₅₀ (average) acrylate)

[0057] SWM 5=Unilin™ 350A (C₂₅ (average) acrylate)

[0058] SWM 6=Unilin™ 350MA (C₂₅ (average) methacrylate)

[0059] SWM 7=Unilin™ 425A (C₃₅ (average) acrylate)

[0060] SWM 8=Behenyl Acrylate

[0061] SWM 9=Unithox™ 450A (C₃₀ (average)-b-(CH₂CH₂O)₁₀ ₅ (average)acrylate)

[0062] SWM 10=Unithox™ 450MA (C₃₀ (average)-b-(CH₂CH₂O)₁₀ ₅ (average)methacrylate)

[0063] DISP 1=Unilin™ 450 ethoxylate

[0064] DISP 2=Unilin™ 550 ethoxylate

[0065] IBOMA=isobornyl methacrylate

[0066] Preparation of Polymer Using Process 1 (Solution/Slurry).

[0067] A mixture of 75.0 grams of SWM 4 and 131.3 grams of heptane washeated to form a solution. The solution was stirred magnetically andallowed to cool. During cooling, SWM crystals precipitated from thesolution. When the temperature had dropped to 50° C.-60° C. there wasadded 150.0 grams of butyl acrylate. The solution temperature dropped to40° C. One hundred fifty grams of methyl methacrylate was then added tothe solution. The temperature of the solution dropped to 30° C. Themixture was allowed to cool to room temperature to give an easilystirrable slurry. An initiator solution was prepared using 6.3 grams ofLupersol 575 (t-amylperoxy 2-ethylhexanoate) and 26.6 grams of heptane.

[0068] A 25.3 gram portion of the monomer slurry and 39.2 grams heptanewere weighed into a 1-liter 4-necked flask fitted with a C-stirrer,thermocouple, N₂ inlet, and separate feed lines for monomer slurry andinitiator solution. This mixture was stirred with a N₂ blanket andheated until a gentle reflux began at approximately 85° C. A 2.1 gramportion of the initiator solution was then added. A clear, pale yellowsolution resulted. After a ten minute hold, simultaneous feeds ofmonomer slurry and initiator solution were begun and enough heat wasapplied to maintain gentle reflux of the solution. After three hours atotal of 269.1 grams of the monomer slurry had been fed and thetemperature had reached 102° C. Both feeds were stopped for 15 minutes,then the remainder of the initiator solution was fed over 25 minutes.Following a 15 minute hold, the mixture was allowed to cool to roomtemperature. The polymer crystallized to give a crumbly solid which was65% polymer, 35% heptane. A portion of this solid was vacuum dried atambient temperature to give neat polymer chunks. Alternatively, aportion of the 65% solid material was diluted to approximately 30%solids with additional heptane, reheated to form a clear solution, thencooled to 7° C. with stirring, vacuum filtered and air dried on aBuchner funnel to give solid polymer chunks similar to those obtained byvacuum drying the 65% solid material.

[0069] Preparation of Polymer by Process 2 (Suspension Polymerization)

[0070] To 0.75 gram NaH₂PO₄.2H₂O in a 500 ml 4-neck flask was added100.0 grams deionized water and 3.75 grams of a 22.5% aqueous solutionof dispersant EM-2B (methacrylic acid copolymer sodium salt) to give aclear solution pH 6.7. To the clear solution was then added 32.0 gramsof butyl methacrylate and 10.0 grams of SWM 1. This mixture was stirredslowly with a N₂ sweep and heated to gentle reflux until the SWM 1melted and dissolved to make a nearly clear solution, then cooled to 56°C. A solution of 0.53 grams of 95% Lupersol 575 in 8.0 grams of butylmethacrylate was then added. The stirring rate was increased and themixture reheated to 95° C. over 10 minutes. The solution was stirred atthat temperature for 2 hours, then allowed to cool. The polymer beadswere collected by filtration, rinsed with deionized water, and allowedto dry at room temperature.

[0071] Characterization of the beads: The percent solids (30 minutes @150° C.) was 99.1 (average). The actual yield of polymer solids was 48.9grams or 97.7% of theory. The residual acrylic monomer was 2969 ppm BMAas determined by Gas Chromatography (“GC”). The portion of the polymersolids soluble in tetrahydrofuran at room temperature was 78%. The beadsflowed together to form a film when heated at 150° C. DSC of the polymershowed a Glass Transition Temperature (“Tg”) of 28° C. and a single melttemperature of 67° C. The latter was an indication that the SWM wasevenly incorporated into the acrylic polymer.

[0072] Preparation of Polymer by Process 3 (Solution)

[0073] A 1 liter reaction vessel was fitted with a thermocouple, atemperature controller, a purge gas inlet, a water-cooled refluxcondenser with purge gas outlet, a stirrer, an Insta-Therm jacketedaddition funnel, and a non-jacketed addition funnel. To the non-jacketedaddition funnel was fed Monomer Mix ‘A’ which contained 316.34 grams ofa homogeneous mixture of 122.50 grams butyl acrylate (100% purity),192.76 grams methyl methacrylate (99.85% purity), 0.70 grams Lupersol575, and 0.35 grams dodecyl mercaptan. To the jacketed addition funnelwhich was heated to and maintained at 90° C. to 100° C. was fed MonomerMix ‘B’ which contained 56.88 grams of a homogeneous mixture of 43.76grams SWM 4 (80.0% purity), and 17.50 grams toluene.

[0074] Ten percent (31.63 grams) of Monomer Mix ‘A’, 10 percent (6.13grams) of Monomer Mix ‘B’, and 87.50 grams toluene were fed to thereaction vessel which was then flushed with nitrogen for 30 minutesbefore applying heat to bring the contents of the reaction vessel to 95°C. When the contents of the vessel reached 95° C., the balance of bothMonomer Mix ‘A’ and ‘B’ were uniformly fed to the reaction vessel over60 minutes. At the end of the monomer mixture addition, the reactionvessel contents were maintained at 95° C. for 30 minutes. At the end ofthe 30 minute hold, the polymerization temperature was increased to 100°C. before starting a feed which contained 1.40 grams of Lupersol 575 and35.00 grams toluene. The feed was added uniformly over a 60 minuteperiod. At the end of the feed the batch was held at 100° C. for 60minutes. At the end of the 60 minute hold, vacuum was applied andtoluene was removed from the batch. The batch was eventually subjectedto a vacuum of 25 mm Hg at 120° C. for 1 hour. The product so formedexhibited a polymer solids content of 97.8 weight % (by GPC), and amolecular weight (Mw) of 341,000.

[0075] Preparation of Polymer by Process 4 (Batch DispersionPolymerization)

[0076] SWM 2 (25 grams) was dissolved in 75 grams styrene at 80° C. to85° C. After the solution became uniform, 150 grams butyl acrylate,preheated to 80° C., was added to the solution. The mixture was agitatedto keep it uniform. In a separate container, 200 grams deionized waterand 2.5 grams of a 60% surfactant aqueous solution of Rhodapex CO436were heated to 90° C. The monomer solution was added to thewater/surfactant solution and homogenized at 15,000 rpm for several 30seconds on-off cycles until the monomer emulsion turned thick.

[0077] While preparing the above monomer emulsion, 800 grams ofdeionized water was heated to 80° C. in a 3-liter round bottom flaskwith a condenser, a thermocouple, a mechanical stirrer and a nitrogengas inlet, to provide a positive pressure of nitrogen flow in the headspace of the reactor. The hot monomer emulsion was poured into thereactor followed by addition of 0.7 gram t-butylperoctoate. The reactionmixture was kept at 80° C. for 4 hours while agitated. At the end of thereaction, the mixture was cooled to room temperature.

[0078] Preparation of Polymer by Process 5 (Semi-Continuous DispersionPolymerization)

[0079] SWM 5 (60 grams) and polyethylene-b-polyethyleneoxide dispersingaid DISP 1 (6 grams) were mixed together and heated until melted. Underagitation a mixture consisting of 528 grams butyl acrylate, 12 gramsmethacrylic acid and 3 grams n-dodecyl mercaptan was then added to theSWM 5 and DISP 1 mixture. The solution was heated at 85° C. and stirreduntil uniform. In a separate container, 600 grams deionized water and21.4 grams of a 28% surfactant (sodium lauryl sulfate) aqueous solutionwere heated to 90° C. The hot monomer solution and the hot watersurfactant solution were mixed and homogenized at 15,000 rpm for several30 seconds on-off cycles until the monomer emulsion turned thick. Afterthe monomer emulsion was cooled to below 40° C. under gentle stirring, 2grams of t-butylperoctoate was added to the monomer emulsion and stirredfor at least 10 minutes.

[0080] While preparing the above monomer emulsion, 200 grams deionizedwater was heated to 85° C. in a 3-liter round bottom flask with acondenser, a thermocouple, a mechanical stirrer and a nitrogen gasinlet, to provide a positive pressure of nitrogen flow in the head spaceof the reactor. Half of the monomer emulsion was added to the reactor.The mixture was allowed to react for 30 minutes. Then the second half ofthe monomer emulsion was gradually added into the reactor through a pumpinto the reactor in 2 hours. After the completion of the monomeremulsion feed, the reaction mixture was held at 85° C. for 1 hour andthen cooled to room temperature.

[0081] The following were prepared by the processes described above:Process Made Sample Composition By  1 1 DISP 1/ 2 MAA/ 88 BA/ 10 SWM 5 5 2 1 DISP 1/ 2 MAA/ 88 EHA/ 10 SWM 5 5  3 1 DISP 2/ 29 IBOMA/ 2 MAA/ 59BA/ 10 SWM 2 5  4 30 Sty/ 60 BA/ 10 SWM 1 4  5* 33 Sty/ 67 BA 4  6 30Sty/ 59 BA/ 1 MAA/ 10 SWM 1 4  7 15 Sty/ 73 BA/ 2 MAA/ 10 SWM 1 4  8 40Sty/ 5 MMA/ 10 BA/ 5 MAA/ 40 SWM 2 4  9 25 Sty/ 30 MMA/ 20 BA/ 25 SWM 24 10 26 Sty/ 52 BA/ 2 MAA/ 20 SWM 2 4 11 20 Sty/ 58 BA/ 2 MAA/ 20 SWM 24 12 29 Sty/ 59 BA/ 2 MAA/ 10 SWM 9 4 13* 88.9 BA/ 11.1 AA 3 H 14 80 BA/10 MAA/ 10 SWM 1 3 H 15 80 BA/ 10 MMA/ 10 SWM 1 3 H 16 78 BA/ 10 MMA/ 2AA/ 10 SWM 1 3 H 17 83 BA/ 10 MMA/ 2 AA/ 5 SWM 1 3 H 18 83 BA/ 10 MMA/ 2AA/ 5 SWM 3 3 H 19 83 BA/ 10 MMA/ 2 AA/ 5 SWM 10 3 H 20 83 BA/ 10 MMA/ 2AA/ 5 SWM 6 3 H 21* 40 BA/ 60 MMA 3 22* 35 BA/ 65 MMA 3 23* 30 BA/ 70MMA 3 24* 25 BA/ 75 MMA 3 25 40 BA/ 55 MMA/ 5 SWM 4 3 26 35 BA/ 60 MMA/5 SWM 4 3 27 30 BA/ 65 MMA/ 5 SWM 4 3 28 50 BA/ 40 MMA/ 10 SWM 4 3 29 45BA/ 45 MMA/ 10 SWM 4 3 30 40 BA/ 50 MMA/ 10 SWM 4 3 31 35 BA/ 55 MMA/ 10SWM 4 3 32 30 BA/ 60 MMA/ 10 SWM 4 3 33 50 BA/ 30 MMA/ 20 SWM 4 3 34 45BA/ 35 MMA/ 20 SWM 4 3 35 40 BA/ 40 MMA/ 20 SWM 4 3 36 35 BA/ 45 MMA/ 20SWM 4 3 37 30 BA/ 50 MMA/ 20 SWM 4 3 38* 40 BA/ 60 SWM 4 3 39* 40 BA/ 60SWM 2 3 40* 40 BA/ 60 SWM 7 3 41* 40 BA/ 60 SWM 5 3 42 60 BA/ 40 SWM 7 343 60 BA/ 40 SWM 5 3 44 80 BA/ 20 SWM 7 3 45 80 BA/ 20 SWM 5 3 46* 45BA/ 55 MMA 3 47 47 BA/ 43 MMA/ 10 SWM 1 3 H 48 10 Sty/ 33 MMA/ 47 BA/ 10SWM 2 4 49* 40 BA/ 60 SWM 8 3 50 60 BA/ 40 SWM 8 3 51 80 BA/ 20 SWM 8 352 90 BA/ 10 SWM 8 3 53 90 BA/ 10 SWM 5 3 54 90 BA/ 10 SWM 7 3 55 80BMA/ 20 SWM 1 2 56 80 BMA/ 20 SWM/ 1 nDDM 2 57 60 BMA/ 40 SWM 1 2 58 60BMA/ 40 SWM 1/ 1 nDDM 2 59 60 BMA/ 40 SWM 1/ 2 nDDM 2

[0082] Adhesive Testing

[0083] An ASTM Tape Test was used to determine adhesion (D 3359-90). Thesubstrates were thermoplastic polyolefin (TPO): Dexter D/S 756-67 andpolypropylene (PP): Himont SB 823. Plaques were wiped gently withisopropanol. Samples were drawndown using a wire-wound rod, then heatedat 50° C. for 30 minutes. The samples were dried in a constanttemperature room for 1 week prior to testing for adhesion. The resultsare shown in Table 1. TABLE 1 Sample TPO PP 47 5 4.5  5* 0 1  6 2 2

[0084] The data above shows the polymers of the invention are useful asadhesives, even on substrates where good adhesion is normally difficultto obtain.

Water Repellents for Nonwovens and Textiles

[0085] Polymer compositions of this invention were used as binders informulations for treating fabric. The polymers were added to theformulations at 10% by weight. The formulations were padded on a BirchBrothers padder at a pressure of 0.17 MPa and a speed of 8 meters perminute. The binder add-on was 6% by weight. The samples were dried in aMathis oven at 150° C. for 4 minutes.

[0086] The dried samples were evaluated using AATCC Test Method 22-1980Water Repellency Spray Test. The results are shown in Table 2. TABLE 2Sample Rating Control (No Formulation Padded) 0 48 80 11 70

[0087] The data above indicate that the polymers of this invention areuseful as water repellents in nonwoven and textile applications.

Wax Replacement in Floor Polish Testing

[0088] The following floor polish formulation was used to test thepolymer composition of the invention. The acrylic binder/alkalineswellable resin/wax ratio in this formulation is 75/10/15. Equal weightof the polymer composition of the invention was substituted forcommercial waxes Epolene®E-43N and Poly Emulsion®325N35. For the no waxcontrol sample, the Rhoplex 1421 level was increased on an equal weightbasis to account for the removal of Epolene®E043N and PolyEmulsion®325N35. Material In Order Of Addition Percent by Weight Water30.73 Kathon ®CG/ICP 0.03 Acrysol ®644 (42%) 5.52 Fluorad ® FC-129 (50%)0.02 Diethylene Glycol Ethyl Ether 5.78 Tripropylene Glycol Methyl ether1.02 Rhoplex ®1421 (38%) 45.76 Epolene ® E-43N (40%) 4.35 Poly Emulsion324N35(35%) 4.97 SE-21 0.02

[0089] The floor polish was coated on black vinyl (B.V.) for the labgloss test and on black vinyl composition tile (B.V.C.) for lab blackheel mark and scuff tests. The floor test was done on commercial vinylfloor tiles.

[0090] Black Heel Mark and Scuff Resistance Test:

[0091] The lab test is described in Chemical Specialty ManufacturersAssociation Bulletin No. 9-73 with rubber shoe heels substituted inplace of rubber cubes. The Rating scale was 1-10 with 10 being bestperformance. The floor test was evaluated on marks made by pedestriantraffic in commercial buildings.

[0092] Static Coefficient of Friction (S.C.O.F.):

[0093] The S.C.O.F. was determined by the James Friction Testing Machinebased on an average of four readings.

[0094] Gloss:

[0095] Gloss was determined by the ASTM D1455 method.

[0096] The results of the tests described above are shown in Tables 3and 4. TABLE 3 Sample Particle Size Gloss Black Mark Scuff S.C.O.F. 4257 10/41 6 4, light 0.83 PE Wax* 150 16/49 8 7 0.54 No Wax* NA 18/52 65 0.90

[0097] TABLE 4 Sample P.S. B.V. B.V.C. Black Mark Scuff S.C.O.F. 12 24069/89 19/49 5 6 0.78 11 375 39/73 11/41 8, light 7 0.72  9 326 18/42 7/29 5 9 0.77 10 351 16/44  7/30 5, light 6 0.74  8 418  9/31  3/17 6 90.74 PE* 150 76/90 19/49 9 8 0.64

[0098] Samples 4, 11 and 12 were further tested in a high traffichallway which was burnished with an UHS Tan Buffer Pad on a 2000 rpmpropane floor burnishing machine periodically. The results are shown inTables 5 and 6. TABLE 5 Sample I.G. Burn. 1 week 2 weeks 3 weeks ScuffB.M. 4 21/65 64 26/46 47/73 54/55 8 9 PE* 30/69 91 23/34 27/68 42/51 9 8

[0099] TABLE 6 Sample I.G. Burn. 1 week 1 week* 2 weeks 2 week* Scuff 128 87 53 6 9 10 8/7 11 5 (hazy) 64 26 7 9 16 8/7 PE* 9 91 54 8 9 12 9/8

[0100] The data above demonstrates that the compositions of thisinvention responded well to floor burnishing due to their crystallinity.

Dry Powder Coatings

[0101] The polymer compostions of this invention were tested forusefulness as dry powder coating compositions. The polymers were groundusing a ScienceWare Micro Mill™ grinder. One gram of each dry polymerpowder was placed in an aluminum weighing pan. The rest of the drypolymer powder was stored in a jar at room temperature. The roomtemperature samples were checked to see if they remained free flowingpowders after 24 hours storage. The samples in the weighing pans wereplaced in ovens at 120° C., 140° C., and 150° C. to determine at whattemperature and time would the dry polymer powder form a film. For drypolymer powder coatings, a film forming temperature in the range of 120°C. to 150° C. is acceptable, but the time to form a film is preferablyless than 3 hours. The powder stability and time to form a film resultsare shown in Table 7. TABLE 7 Powder Sample Stability 120° C. 140° C.150° C.  21* S >3 hours    2.5 hours NT  22* Good >3 hours    2.5 hoursNT  23* Good >3 hours   >3 hours   2.5 hours  24* Good >3 hours   >3hours   2.5 hours 25 Good >3 hours   >3 hours   2.5 hours 26 Good >3hours   >3 hours   2.5 hours 27 Good >3 hours   >3 hours   >3 hours 28 S<0.5 hours NT NT 29 Good 1 hour NT NT 30 Good 1.5 hours NT NT 31 Good >3hours   1.25 hours NT 32 Good >3 hours   >3 hours   2.5 hours 33 Good0.75 hours NT NT 34 Good 0.75 hours NT NT 35 Good 0.75 hours NT NT 36Good 1.75 hours NT NT 37 Good 1.75 hours NT NT 38 Good <0.5 hours NT NT39 Good <0.5 hours NT NT 40 Good <0.5 hours NT NT 41 Good <0.5 hours NTNT 42 Good <0.5 hours NT NT 43 T NT NT NT 44 T NT NT NT 45 T NT NT NT 55G NT NT <0.5 hours 56 S NT NT <0.5 hours 57 G NT NT <0.5 hours 58 G NTNT <0.5 hours 59 G NT NT <0.5 hours

[0102] The data above indicates that the polymers of this invention areuseful as dry powder coating compositions.

[0103] Some of the properties of the polymers of this invention werecompared to polymers with greater than 50 percent by weight syntheticwax monomer incorporation. The data are shown in Table 8. TABLE 8Sample/Rating SWM/BA C₂₀ C₂₅ C₃₅ C₄₀ C₅₀ 60/40 49/P 41/P 40/P 39/P  38/P40/60 50/T 43/S 42/P 57/P* NT 20/80 51/T 45/T 44/S 55/P* NT 10/90 52/T53/T 54/T NT NT

[0104] The data above demonstrates that polymers with greater than 50percent by weight synthetic wax monomer incorporation form dry powdersand are non-tacky regardless of the length of the carbon chain on thesynthetic wax monomer. The synthetic wax monomer is significantly moreexpensive than butyl acrylate and other monomers incorporated in thepolymers of this invention. Therefore, it is desirable to reduce theamount of synthetic wax monomer below 60 percent by weight withoutsacrificing the dry powder polymer properties. The data above shows thatthe dry powder polymer properties at 60 percent synthetic wax monomerincorporation may be retained at 40 percent incorporation by increasingthe length of the carbon chain on the synthetic wax monomer. The datasuggests that it may be possible to reduce the percent incorporation ofsynthetic wax monomer to between 10 and 20 percent by weight withoutsacrificing dry powder polymer properties.

Hot Melt Sealant

[0105] The polymer compositions of this invention were tested as hotmelt sealants by applying the solid polymers to glass and vinylsubstrates. The samples were heated in an oven to 80° C., 90° C., and115° C. The heated polymers were checked to see how well they melted ateach temperature. A nylon screen was applied over each melted polymer.The polymer was cooled and tested for adhesion with an Instron machinepulling the screen away from the polymer coated substrate. The resultsare shown in Table 9. TABLE 9 Melt Behavior Adhesion (kg/m) Sample 80°C. 90° C. 115° C. Glass Vinyl  13* Poor Poor Poor NT NT 14 Poor PoorPartial 214-321 C A 15 Partial Good Good  5 A C 16 Partial Partial Good18-36 A A 17 Partial Good Good 125-143 C C 18 Poor Partial Good 179-250C A/C 19 Partial Partial Good NT C 20 Good Good Good 71 A A

[0106] The data above indicate that the polymers of this invention areuseful as hot melt sealants.

Wood Treatment

[0107] The polymer compositions of this invention were applied to woodboards and tested for utility as water repellents for wood applications.Matched sapwood boards measuring 1.8 cm×1.8 cm×1.8 cm(tangential×radial×logitudinal) were used for this test. The wood wasstraight grained, flat sawn, clear with 6 to 10 rings per 2.5 cm, and40% to 50% summerwood. Samples were cut with a fine tooth saw to obtainas smooth a surface as possible. The polymer compositions and controlwood treatment compositions were applied to the wood boards by pressuretreatment. For each level (weight percent) of coating compositiontested, two wood boards were coated with the polymer of this invention.The coated wood was dried for two weeks.

[0108] Samples were conditioned for 10 days at 45% relative humidity.The sample weights were checked until constant to insure moistureequilibrium. Samples were weighed to the nearest 0.001 grams. Sampleswere tested using a Dynamic Swellometer apparatus that records swell inthousands of an inch. The instrument automatically measures Swell Valuesduring the test. Samples were measured (radial, tangential, longitudinaldimensions) using a micrometer and the measurements were recorded.Samples were placed radially in a swell chamber and secured so that nofloating could occur during testing. Samples were then covered withdistilled water and tested for 100 minutes. Immediately after testing,the samples were removed and weighed to the nearest 0.001 gram. Sampleswere again measured (radial, tangential, longitudinal dimensions) usinga micrometer and the measurements were recorded.

[0109] Water Repellency Efficiency (“WRE”) was measured following thefollowing formula:${\% \quad W\quad R\quad E} = {\frac{A - B}{A} \times 100}$

[0110] A=10 or 100 minute Control Swell Value

[0111] B=10 or 100 minute Polymer Of Invention Swell Value

[0112] The first wood board was sampled 4 times. The second wood boardwas sampled 2 times. The results of the tests were averaged. The resultsare shown in TABLE 10 Average % WRE Coating Level (Weight %) 10 Minutes60 Minutes Wax* 0.6   87   51 CCA/Wax* 0.6/0.6   83   53 4 1   72   412.5   91   59 5   82   44 7 1 −32 $ −37 $ 2.5   77   35 5   93   70

[0113] The data above shows that the polymers of this invention providegood water resistance and are suitable for wood treatment applications.

We claim:
 1. A polymer comprising as polymerized units: A) from 1 toless than 50 percent by weight of a synthetic wax monomer of formula I:

wherein R₁ is selected from H and CH₃, R₂ is selected from H and C₁-C₅alkyl, R₃ is selected from H and CH₃, n=9-115, and m=0-1370; and B) from50 to 99 percent by weight of at least one second monomer.
 2. Thepolymer according to claim 1 wherein the synthetic wax monomer offormula I is present at from 3 to 45 percent by weight and the at leastone second monomer is present at from 55 to 97 percent by weight.
 3. Thepolymer according to claim 1 wherein the synthetic wax monomer offormula I is present at from 4 to 40 percent by weight and the at leastone second monomer is present at from 60 to 96 percent by weight.
 4. Thepolymer according to claim 3 wherein the at least one second monomer isselected from (meth)acrylic acid, esters of (meth)acrylic acid,(meth)acrylic amides, vinyl aromatic monomers, substituted ethylenemonomers, functional monomers with a post crosslinkable group,multifunctional monomers, and mixtures thereof
 5. A method of preparinga polymer comprising: 1) forming a slurry by cooling a solutioncontaining a synthetic wax monomer and a solvent; 2) forming a reactionmixture by admixing at least one second monomer with the slurry; and 3)polymerizing the reaction mixture in the presence of an initiator.
 6. Amethod of preparing a polymer comprising: dissolving a synthetic waxmonomer in at least one second monomer to form a solution; admixingwater and at least one surfactant to provide a second solution; forminga monomer emulsion by admixing the first and second solutions; providinga reactor with heated water; and polymerizing the monomer emulsion byadding the monomer emulsion and at least one initiator to the reactor.7. A method of coating comprising: applying a composition containing thepolymer of claim 1 to a substrate.
 8. The method according to claim 7wherein the synthetic wax monomer of formula I is present at from 3 to45 percent by weight and the at least one second monomer is present atfrom 55 to 97 percent by weight.
 9. The method according to claim 7wherein the synthetic wax monomer of formula I is present at from 4 to40 percent by weight and the at least one second monomer is present atfrom 60 to 96 percent by weight.
 10. A method of use of a polymer as anadhesive comprising: forming a first polymer coated substrate byapplying a polymer of claim 1 to a substrate and applying a secondsubstrate to the first polymer coated substrate.